Methods for gasification of carbonaceous materials

ABSTRACT

The present disclosure is generally directed to process of gasification of carbonaceous materials to produce synthesis gas or syngas. The present disclosure provides improved methods of gasification comprising adding a molecular oxygen-containing gas and optionally adding water into said gasifier. This disclosure is also directed to process of production of one or more alcohols from said syngas via fermentation or digestion in the presence of at least one microorganism.

FIELD

The present disclosure is generally directed to process of gasificationof carbonaceous materials to produce synthesis gas or syngas. Thisdisclosure is also directed to process of production of one or morealcohols from said syngas via fermentation or digestion in the presenceof at least one microorganism.

BACKGROUND

The present disclosure contemplates production of synthesis gascomprising carbon monoxide (CO), carbon dioxide (CO₂), and hydrogen (H₂)via gasification of carbonaceous materials. Synthesis gas can be used toproduce one or more chemicals through biological or chemical routes.Synthesis gas can also be used to produce energy to generateelectricity.

Thus syngas can be acted upon by fermentation or digestion by certainmicroorganisms to produce alcohols (methanol, ethanol, propanol,butanol, etc.), acetic acid, acetates, hydrogen, etc. Various strains ofacetogens have been described for use in the production of liquid fuelsfrom syngas: Butyribacterium methylotrophicum, Clostridiumautoethanogenum, Clostridium carboxidivorans, Clostridium ljungdahlii,Clostridium ragsdalei.

U.S. Pat. No. 5,173,429 to Gaddy et al. discloses Clostridiumljungdahlii ATCC No. 49587, an anaerobic microorganism that producesethanol and acetate from synthesis gas. U.S. Pat. No. 5,807,722 to Gaddyet al. discloses a method and apparatus for converting waste gases intouseful products such as organic acids and alcohols using anaerobicbacteria, such as Clostridium ljungdahlii ATCC No. 55380. U.S. Pat. No.6,136,577 to Gaddy et al. discloses a method and apparatus forconverting waste gases into useful products such as organic acids andalcohols (particularly ethanol) using anaerobic bacteria, such asClostridium ljungdahlii ATCC Nos. 55988 and 55989. U.S. Pat. No.6,136,577 to Gaddy et al. discloses a method and apparatus forconverting waste gases into useful products such as organic acids andalcohols (particularly acetic acid) using anaerobic strains ofClostridium ljungdahlii. U.S. Pat. No. 6,753,170 to Gaddy et al.discloses an anaerobic microbial fermentation process for the productionof acetic acid. U.S. Pat. No. 7,285,402 to Gaddy et al. discloses ananaerobic microbial fermentation process for the production of alcohol.

US Patent Application No. 20070275447 discloses a clostridia bacterialspecies (Clostridium carboxidivorans, ATCC BAA-624, “P7”) that iscapable of synthesizing, from waste gases, products which are useful asbiofuel. US Pat. Appl. No. 20080057554 discloses a clostridia bacterialspecies (Clostridium ragsdalei, ATCC BAA-622, “P11”) that is capable ofsynthesizing, from waste gases, products which are useful as biofuel.

WO 2007/117157 discloses methods of anaerobic fermentation processesthat produce acetate as a by-product in addition to a desired product,and that can utilize hydrogen and/or carbon dioxide in the fermentation.In this disclosure fermentation is carried out by one or more strains ofbacteria selected from Clostridium, Moorella and Carboxydothermus. WO2009/064200 discloses a class of bacteria which has improved efficiencyin the production of ethanol by anaerobic fermentation of substratescontaining carbon monoxide. As disclosed, the exemplified bacterium,Clostridium autoethanogenum, is capable of producing ethanol andacetate.

Syngas can be converted to various chemicals and fuels using chemicalcatalytic routes such as process using catalysts containing copper (Cu)and zinc (Zn) to make methanol or mixed alcohols, process usingcatalysts containing cobalt (Co) and rhodium (Rh) to produce ethanol andFischer-Tropsch type synthesis to make olefins, etc. WO 2009/035851discloses methods of converting syngas into ethanol and/or other higheralcohols using reactors comprising catalyst capable of converting syngasto alcohols said catalyst comprising at least one Group IB element, atleast one Group IIB element, and at least one Group IIIA element.

WO 2010/002618 discloses a method for making alcohols from a gascomprising hydrogen and carbon monoxide comprising: passing the gasthrough a reactor containing a carried catalyst comprising elementalmolybdenum, cobalt and an alkali or alkaline earth metal, and/orhydrides thereof.

Production of chemicals or power in general depends upon the quality ofsyngas produced, e.g. amount or concentration of carbon monoxide (CO)and hydrogen (H₂) in syngas as well as the ratio of carbon monoxide tohydrogen (CO/H₂).

A widely used process of gasification of carbonaceous materials toproduce syngas rich in carbon monoxide (CO) and hydrogen (H₂) uses anoxygen-deficient or oxygen-starved atmosphere in the gasifier thatprevents complete conversion of carbon in the carbonaceous material.However, under oxygen-starved condition part of the carbon content ofthe carbonaceous materials often remains as un-reacted carbon particlesor soot in the product syngas. Another part of the carbon content of thecarbonaceous materials remains as un-reacted carbon in ash.

Incomplete conversion of carbonaceous feedstock to carbon monoxide (CO)and hydrogen (H₂) means less available carbon monoxide (CO) and hydrogen(H₂) for production of power or chemicals (e.g. alcohols). Increasedamount of un-reacted or unconverted carbon particles or soot in the rawsyngas increases difficulty and cost of cleaning up syngas. Increasedamount of un-reacted carbon in ash increases processing difficulty andcost of disposal of ash.

It would be desirable to have a method of operation of gasifier thatmaximizes production of power or chemicals from the syngas produced fromgasifier while keeping amount of un-reacted or unconverted carbonparticles in the raw syngas under desirable low values.

It would be desirable to have a method of operation of gasifier thatmaximizes production of power or chemicals from the syngas produced fromgasifier while keeping amount of un-reacted or unconverted carbonparticles in the raw syngas and amount of un-reacted carbon in ash underdesirable low values.

It would be desirable to have a method of operation of gasifier thatmaximizes production of power or chemicals from the syngas produced fromgasifier while keeping amount of soot in the raw syngas under desirablelow values.

It would be desirable to have a method of operation of gasifier thatmaximizes production of power or chemicals from the syngas produced fromgasifier while keeping amount of soot in the raw syngas and amount ofun-reacted carbon in ash under desirable low values.

The present disclosure provides various new and desirable gasifierdesigns and methods of operating a gasifier that are not known in theart. The present disclosure accomplishes the needs described above.

SUMMARY

The present disclosure provides a method of gasification of carbonaceousmaterials in a gasifier to produce a product gas comprising carbonmonoxide, hydrogen, and tar; said method comprising: adding one or morecarbonaceous materials, adding a molecular oxygen-containing gas andoptionally adding water into said gasifier; wherein amount of totaloxygen added to said gasifier in pounds per pound of total carbon addedto said gasifier comprises greater than about 0.75. In one embodimentamount of total oxygen added to said gasifier in pounds per pound oftotal carbon added to said gasifier comprises about 0.75 to about 3.0.As an embodiment, the present disclosure further comprising treatingsaid product gas at a temperature of about 1750° F. to about 3500° F. inthe presence of molecular oxygen to produce a raw syngas comprisingcarbon monoxide, hydrogen, and syngas-carbon. In one embodiment rawsyngas also comprises carbon dioxide.

As an embodiment the present disclosure provides a method ofgasification of carbonaceous materials in a gasifier to produce syngasusing partial oxidation method; said gasifier comprising a firstreaction zone and a second reaction zone; said method comprising: addingone or more carbonaceous materials into said first reaction zone ofgasifier; adding a molecular oxygen containing gas and optionally addingwater or steam into one or both of said first reaction zone and secondreaction zone of said gasifier; wherein amount of total oxygen added tosaid gasifier in pounds per pound of total carbon added to said gasifiercomprises greater than about 1.25. In one embodiment amount of totaloxygen added into said first reaction zone of said gasifier in poundsper pound of total carbon added to said gasifier comprises about 1.25 toabout 3.5.

As an embodiment the present disclosure provides a method ofgasification of carbonaceous materials in a gasifier to produce syngas;said gasifier comprising a first reaction zone and a second reactionzone; said method comprising: adding one or more carbonaceous materialsinto said first reaction zone of gasifier; adding a molecular oxygencontaining gas and optionally adding water or steam into one or both ofsaid first reaction zone and second reaction zone of said gasifier;wherein amount of total oxygen added to said gasifier in pounds perpound of total carbon added to said gasifier comprises greater thanabout 1.25. In one embodiment amount of total oxygen added into saidfirst reaction zone of said gasifier in pounds per pound of total carbonadded to said gasifier comprises about 1.25 to about 3.5.

The present disclosure provides a method further comprising: subjectingsaid raw syngas to cooling and cleaning up to produce a clean syngas;contacting said clean syngas with a biocatalyst in a fermentationcontainer to produce an alcohol product mixture.

In one embodiment carbon to hydrogen mass ratio in one or more of saidcarbonaceous materials comprises 1 to 20. In one embodiment carbon tooxygen mass ratio in one or more of said carbonaceous materialscomprises 1 to 200.

The present disclosure provides a method of gasification of carbonaceousmaterials in a gasifier to produce syngas using partial oxidationmethod; said gasifier comprising a first reaction zone, a secondreaction zone and a chamber connecting first reaction zone to secondreaction zone; said method comprising: adding one or more carbonaceousmaterials into said first reaction zone of gasifier; adding a molecularoxygen containing gas and optionally adding water or steam into one orboth of said first reaction zone and second reaction zone of saidgasifier; comprising adding molecular oxygen containing gas into saidchamber connecting said first reaction zone with said second reactionzone of said gasifier.

The present disclosure provides a gasifier to produce syngas usingpartial oxidation method; said gasifier comprising a first reactionzone, a second reaction zone and a chamber connecting first reactionzone to second reaction zone; said method comprising: adding one or morecarbonaceous materials into said first reaction zone of gasifier; addinga molecular oxygen containing gas and optionally adding water or steaminto one or both of said first reaction zone and second reaction zone ofsaid gasifier; comprising adding molecular oxygen containing gas intosaid chamber connecting said first reaction zone with said secondreaction zone of said gasifier.

The present disclosure provides a method of gasification of carbonaceousmaterials in a gasifier to produce syngas; said gasifier comprising afirst reaction zone, a second reaction zone and a chamber connectingfirst reaction zone to second reaction zone; said method comprising:adding one or more carbonaceous materials into said first reaction zoneof gasifier; adding a molecular oxygen containing gas and optionallyadding water or steam into one or both of said first reaction zone andsecond reaction zone of said gasifier; comprising adding molecularoxygen containing gas into said chamber connecting said first reactionzone with said second reaction zone of said gasifier.

The present disclosure provides a gasifier to produce syngas; saidgasifier comprising a first reaction zone, a second reaction zone and achamber connecting first reaction zone to second reaction zone; saidmethod comprising: adding one or more carbonaceous materials into saidfirst reaction zone of gasifier; adding a molecular oxygen containinggas and optionally adding water or steam into one or both of said firstreaction zone and second reaction zone of said gasifier; comprisingadding molecular oxygen containing gas into said chamber connecting saidfirst reaction zone with said second reaction zone of said gasifier.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 comprises a schematic diagram illustrating an embodiment of thegasification process for this present disclosure; FIG. 1 presents anembodiment of a two-stage gasification process.

FIG. 2 comprises a schematic diagram illustrating an embodiment of theprocess of producing ethanol via gasification of carbonaceous materials.

FIG. 3 comprises a schematic diagram illustrating an embodiment of theeffect of total oxygen input into gasifier on syngas-carbon for variousamounts of water input into gasifier.

FIG. 4 comprises a schematic diagram illustrating an embodiment of theeffect of total oxygen input into gasifier on amount of ethanol producedfor various amounts of water input into gasifier.

FIG. 5 comprises a schematic diagram illustrating an embodiment of theeffect of total oxygen input into first reaction zone of gasifier onsyngas-carbon for various amounts of water input into gasifier.

FIG. 6 comprises a schematic diagram illustrating an embodiment of theeffect of total oxygen input into first reaction zone of gasifier onamount of ethanol produced for various amounts of water input intogasifier.

DETAILED DESCRIPTION Definitions

Unless otherwise defined, the following terms as used throughout thisspecification for the present disclosure are defined as follows and caninclude either the singular or plural forms of definitions belowdefined:

The term “about” modifying any amount refers to the variation in thatamount encountered in real world conditions, for example, the variationin that amount encountered in real world conditions of sustainingmicroorganism culture, e.g., in the lab, pilot plant, or productionfacility. For example, an amount of an ingredient or measurementemployed in a mixture or quantity when modified by “about” includes thevariation and degree of care typically employed in measuring in anexperimental condition in production plant or lab. For example, theamount of a component of a product when modified by “about” includes thevariation between batches in a multiple experiments in the plant or laband the variation inherent in the analytical method. Whether or notmodified by “about,” the amounts include equivalents to those amounts.Any quantity stated herein and modified by “about” can also be employedin the present disclosure as the amount not modified by “about.”

The term “acetogen” or “acetogenic” refers to a bacterium that generatesacetate as a product of anaerobic respiration. This process is differentfrom acetate fermentation, although both occur in the absence of oxygenand produce acetate. These organisms are also referred to as acetogenicbacteria, since all known acetogens are bacteria. Acetogens are found ina variety of habitats, generally those that are anaerobic (lack oxygen).Acetogens can use a variety of compounds as sources of energy andcarbon; the best studied form of acetogenic metabolism involves the useof carbon dioxide as a carbon source and hydrogen as an energy source.

The term “ash-carbon” or “Ash-carbon” or “Ash-Carbon” means content ofunconverted carbon in ash removed from gasifier.

The term “ash fusion temperature” means temperature at which at least aportion of ash or inorganic matter contained in carbonaceous materialmelts. Typically this temperature comprises about 1400° F.

The term “biocatalyst” means, for the present disclosure, naturalcatalysts, protein enzymes, living cells, microorganisms, and bacteria.

The terms “bioreactor,” “reactor,” or “fermentation bioreactor,” includea fermentation device consisting of one or more vessels and/or towers orpiping arrangement, which includes the Continuous Stirred Tank Reactor(CSTR), Immobilized Cell Reactor (ICR), Trickle Bed Reactor (TBR),Bubble Column, Gas lift Fermenter, Static Mixer, or other devicesuitable for gas-liquid contact. Preferably for the method of thisdisclosure, the fermentation bioreactor comprises a growth reactor whichfeeds the fermentation broth to a second fermentation bioreactor, inwhich most of the product, ethanol, is produced.

“Carbonaceous material” as used herein refers to carbon rich materialsuch as coal, and petrochemicals. However, in this specification,carbonaceous material includes any carbon material whether in solid,liquid, gas, or plasma state. Among the numerous items that can beconsidered carbonaceous material, the present disclosure contemplates:carbonaceous liquid product, carbonaceous industrial liquid recycle,carbonaceous municipal solid waste (MSW or msw), carbonaceous urbanwaste, carbonaceous agricultural material, carbonaceous forestrymaterial, carbonaceous wood waste, carbonaceous construction material,carbonaceous vegetative material, carbonaceous industrial waste,carbonaceous fermentation waste, carbonaceous petrochemical coproducts,carbonaceous alcohol production coproducts, carbonaceous coal, tires,plastics, waste plastic, coke oven tar, fibersoft, lignin, black liquor,polymers, waste polymers, polyethylene terephthalate (PETA), polystyrene(PS), sewage sludge, animal waste, crop residues, energy crops, forestprocessing residues, wood processing residues, livestock wastes, poultrywastes, food processing residues, fermentative process wastes, ethanolcoproducts, spent grain, spent microorganisms, or their combinations.For this disclosure carbon dioxide and methane-containing gas are notconsidered carbonaceous materials. For avoidance of doubt, variouscarbonaceous material(s) can be construed in either the singular orplural form, where appropriate, regardless of singular or plural formword usage as provided in this definition.

The term “fermentation” means fermentation of carbon monoxide (CO) toalcohols and acetate. A number of anaerobic bacteria are known to becapable of carrying out the fermentation of carbon monoxide (CO) toalcohols, including butanol and ethanol, and acetic acid, and aresuitable for use in the process of the present disclosure. Examples ofsuch bacteria that are suitable for use in the disclosure include thoseof the genus Clostridium, such as strains of Clostridium ljungdahlii,including those described in WO 2000/68407, EP 117309, U.S. Pat. Nos.5,173,429, 5,593,886, and 6,368,819, WO 1998/00558 and WO 2002/08438,and Clostridium autoethanogenum. Other suitable bacteria include thoseof the genus Moorella, including Moorella sp HUC22-1, and those of thegenus Carboxydothermus. The disclosures of each of these publicationsare fully incorporated herein by reference. In addition, otheracetogenic anaerobic bacteria may be selected for use in the process ofthe disclosure by a person of skill in the art. It will also beappreciated that a mixed culture of two or more bacteria may be used inthe process of the present disclosure. One microorganism suitable foruse in the present disclosure is Clostridium autoethanogenum that isavailable commercially from DSMZ and having the identifyingcharacteristics of DSMZ deposit number DSMZ 10061. The fermentation maybe carried out in any suitable bioreactor, such as a continuous stirredtank reactor (CTSR), a bubble column reactor (BCR) or a trickle bedreactor (TBR). Also, in some preferred embodiments of the disclosure,the bioreactor may comprise a first, growth reactor in which themicroorganisms are cultured, and a second, fermentation reactor, towhich fermentation broth from the growth reactor is fed and in whichmost of the fermentation product (ethanol and acetate) is produced.

The term “fibersoft” or “Fibersoft” or “fibrosoft” or “fibrousoft” meansa type of carbonaceous material that is produced as a result ofsoftening and concentration of various substances; in an examplecarbonaceous material is produced via steam autoclaving of varioussubstances. In another example, the fibersoft can comprise steamautoclaving of municipal, industial, commercial, medical waste resultingin a fibrous mushy material.

“Gasifier” or “gasifier” means counter-current fixed bed gasifer,co-current fixed bed gasifier, moving bed, fluidized bed gasifier,entrained flow gasifier, plasma arc gasifier, single stage gasifier,multistage gasifier, two stage gasifier, three stage gasifer, four stagegasifier, five stage gasifer, and their combinations.

The term “microorganism” includes bacteria, fungi, yeast, archaea, andprotists; microscopic plants (called green algae); and animals such asplankton, the planarian and the amoeba. Some also include viruses, butothers consider these as non-living. Microorganisms live in all parts ofthe biosphere where there is liquid water, including soil, hot springs,on the ocean floor, high in the atmosphere and deep inside rocks withinthe Earth's crust. Microorganisms are critical to nutrient recycling inecosystems as they act as decomposers. Microbes are also exploited bypeople in biotechnology, both in traditional food and beveragepreparation, and in modern technologies based on genetic engineering. Itis envisioned that mixed strain microorganisms, that may or may notcontain strains of various microorganisms, will be utilized in thepresent disclosure. Also, it is envisioned that directed evolution canselectively screen microorganisms that can be utilized in the presentdisclosure. It is further envisioned that recombinant DNA technology cancreate microorganisms using select strains of existing microorganisms.It is envisioned that acetogenic anaerobic (or facultative) bacteria,which are able to convert carbon monoxide (CO) and water or hydrogen(H₂) and CO₂ into ethanol and acetic acid products will be utilized inthe present disclosure. Useful bacteria according to this disclosureinclude, without limitation, Acetogenium kivui, Acetobacterium woodii,Acetoanaerobium noterae, Butyribacterium methylotrophicum,Caldanaerobacter subterraneus, Caldanaerobacter subterraneus pacificus,Carboxydothermus hydrogenoformans, Clostridium aceticum, Clostridiumacetobutylicum, Clostridium Autoethanogenum, Clostridium thermoaceticum,Eubacterium limosum, Clostridium ljungdahlii PETC, Clostridiumljungdahlii ERI2, Clostridium ljungdahlii C-01, Clostridium ljungdahliiO-52, Clostridium ultunense, Clostridium ragsdalei, Clostridiumcarboxidivorans, Geobacter sulfurreducens, Moorella, Moorellathermacetica, and Peptostreptococcus productus. Other acetogenicanaerobic bacteria are selected for use in these methods by one of skillin the art. In some embodiments of the present disclosure, severalexemplary strains of C. ljungdahlii include strain PETC (U.S. Pat. No.5,173,429); strain ERI2 (U.S. Pat. No. 5,593,886) and strains C-01 andO-52 (U.S. Pat. No. 6,136,577). These strains are each deposited in theAmerican Type Culture Collection, 10801 University Boulevard, Manassas,Va. 20110-2209, under Accession Nos.: 55383 (formerly ATCC No. 49587),55380, 55988, and 55989 respectively. Each of the strains of C.ljungdahlii is an anaerobic, gram-positive bacterium with a guanine andcytosine (G+C) nucleotide content of about 22 mole %. These bacteria usea variety of substrates for growth, but not methanol or lactate. Thesestrains differ in their carbon monoxide (CO) tolerance, specific gasuptake rates and specific productivities. In the “wild” strains found innature, very little ethanol production is noted. Strains of C.ljungdahlii operate ideally at 37.degree. C., and typically produce anethanol to acetyl (i.e. which refers to both free or molecular aceticacid and acetate salts) product ratio of about 1:20 (1 part ethanol per20 parts acetyl) in the “wild” state. Ethanol concentrations aretypically only 1-2 g/L. While this ability to produce ethanol is ofinterest, because of low ethanol productivity the “wild” bacteria cannotbe used to economically produce ethanol on a commercial basis. Withminor nutrient manipulation the above-mentioned C. ljungdahlii strainshave been used to produce ethanol and acetyl with a product ratio of 1:1(equal parts ethanol and acetyl), but the ethanol concentration is lessthan 10 g/L, a level that results in low productivity, below 10 g/L-day.In addition culture stability is an issue, primarily due to therelatively high (8-10 g/L) concentration of acetyl (2.5-3 g/L, molecularacetic acid) in combination with the presence of ethanol. Furthermore,as the gas rate is increased in an effort to produce more ethanol, theculture is inhibited, first by molecular acetic acid and then by carbonmonoxide (CO). As a result, the culture becomes unstable and fails touptake gas and produce additional product. Further, early work by theinventors showed difficulty in producing more than a 2:1 ratio ofethanol to acetyl in a steady state operation. A large number ofdocuments describe the use of anaerobic bacteria, other than C.ljungdahlii, in the fermentation of sugars that do not consume carbonmonoxide (CO), CO₂ and hydrogen (H₂) to produce solvents. In an attemptto provide high yields of ethanol, a variety of parameters have beenaltered which include: nutrient types, microorganism, specific additionof reducing agents, pH variations, and the addition of exogenous gases.

The term “municipal solid waste” or “MSW” or “msw” means wastecomprising household, commercial, industrial and/or residual waste.

The term “syngas” or “synthesis gas” means synthesis gas which is thename given to a gas mixture that contains varying amounts of carbonmonoxide and hydrogen. Examples of production methods include steamreforming of natural gas or hydrocarbons to produce hydrogen, thegasification of coal and in some types of waste-to-energy gasificationfacilities. The name comes from their use as intermediates in creatingsynthetic natural gas (SNG) and for producing ammonia or methanol.Syngas is also used as an intermediate in producing synthetic petroleumfor use as a fuel or lubricant via Fischer-Tropsch synthesis andpreviously the Mobil methanol to gasoline process. Syngas consistsprimarily of hydrogen, carbon monoxide, and very often some carbondioxide, and has less than half the energy density (i.e., BTU content)of natural gas. Syngas is combustible and often used as a fuel source oras an intermediate for the production of other chemicals.

The term “syngas-carbon” or “Syngas-carbon” or “Syngas-Carbon” meanscontent of unconverted carbon particles in raw syngas produced fromgasification process.

The term “total carbon input into gasifier” or “total carbon added intogasifier” means sum of all carbon contained in anything fed into thegasifier, e.g. carbon contained in one or more carbonaceous materials asdefined above added into the gasifier.

The term “total carbon input into first reaction zone of gasifier” or“total carbon added into first reaction zone of gasifier” means sum ofall carbon contained in anything fed into first reaction zone of thegasifier, e.g. carbon contained in one or more carbonaceous materials asdefined above added into first reaction zone of the gasifier.

The term “total oxygen input into gasifier” or “total oxygen added intogasifier” means sum of all oxygen contained in anything fed into thegasifier, e.g. oxygen contained in molecular oxygen containing gas addedinto the gasifier, oxygen contained in one or more carbonaceousmaterials as defined above added into the gasifier, oxygen contained inany water or steam added into the gasifier.

The term “total oxygen input into first reaction zone of gasifier” or“total oxygen added into first reaction zone of gasifier” means sum ofall oxygen contained in anything fed into first reaction zone of thegasifier, e.g. oxygen contained in molecular oxygen containing gas addedinto first reaction zone of the gasifier, oxygen contained in one ormore carbonaceous materials as defined above added into first reactionzone of the gasifier, oxygen contained in any water or steam added intofirst reaction zone of the gasifier.

DETAILED DESCRIPTION

The present disclosure will now be described more fully and withreference to the figures in which various embodiments of the presentdisclosure are shown. The subject matter of this disclosure may,however, be embodied in many different forms and should not be construedas being limited to the embodiments set forth herein.

The present disclosure provides a method of gasification of carbonaceousmaterials in a gasifier to produce a product gas comprising carbonmonoxide, hydrogen, and tar; said method comprising: adding one or morecarbonaceous materials, adding a molecular oxygen-containing gas andoptionally adding water into said gasifier; wherein the amount of totaloxygen added to said gasifier in pounds per pound of total carbon addedto said gasifier comprises greater than about 0.75. In one embodimentamount of total oxygen added to said gasifier in pounds per pound oftotal carbon added to said gasifier comprises about 0.75 to about 3.0.As embodiments, the present disclosure comprises water addition to saidgasifier; comprises direct steam addition into said gasifier; compriseswater addition by partial direct steam addition into said gasifier;comprises adding one or more said carbonaceous materials containingmoisture into said gasifier.

In an embodiment of the present disclosure one or more of saidcarbonaceous materials comprises selection from carbonaceous material,carbonaceous liquid product, carbonaceous industrial liquid recycle,carbonaceous municipal solid waste (MSW or msw), carbonaceous urbanwaste, carbonaceous agricultural material, carbonaceous forestrymaterial, carbonaceous wood waste, carbonaceous construction material,carbonaceous vegetative material, carbonaceous industrial waste,carbonaceous fermentation waste, carbonaceous petrochemical coproducts,carbonaceous alcohol production coproducts, carbonaceous coal, tires,plastics, waste plastic, coke oven tar, fibersoft, lignin, black liquor,polymers, waste polymers, polyethylene terephthalate (PETA), polystyrene(PS), sewage sludge, animal waste, crop residues, energy crops, forestprocessing residues, wood processing residues, livestock wastes, poultrywastes, food processing residues, fermentative process wastes, ethanolcoproducts, spent grain, spent microorganisms, or their combinations. Inone embodiment carbon content of one or more said carbonaceous materialscomprises about 0.25 to about 1.0 pounds per pound of one or more saidcarbonaceous materials on a water free basis. In one embodiment hydrogencontent of one or more said carbonaceous materials comprises about 0.0to about 0.25 pounds per pound of one or more said carbonaceousmaterials on a water free basis. In one embodiment oxygen content of oneor more said carbonaceous materials comprises about 0.0 to about 0.5pounds per pound of one or more said carbonaceous materials on a waterfree basis.

In one embodiment, said carbonaceous material comprises a plurality ofcarbonaceous materials selected from carbonaceous material, carbonaceousliquid product, industrial carbonaceous liquid recycle, carbonaceousmunicipal solid waste (MSW), carbonaceous urban waste, carbonaceousagricultural material, carbonaceous forestry material, carbonaceous woodwaste, carbonaceous construction material, carbonaceous vegetativematerial, carbonaceous petrochemical coproducts, carbonaceous coal,plastic, waste plastic, coke oven tar, fibersoft, tires, lignin, blackliquor, polymers, waste polymers, polyethylene terephthalate (PETA),polystyrene (PS), sewage sludge, animal waste, crop residues, energycrops, forest processing residues, wood processing residues, livestockwastes, poultry wastes, food processing residues, fermentative processwastes, carbonaceous industrial waste, alcohol production wastes,ethanol coproducts, spent grains, spent microorganisms or combinationsof any of these.

In an embodiment, the gasifier produces ash containing ash-carbon andwherein said ash comprises less than about 10% of ash-carbon. In anembodiment the gasifier produces ash containing ash-carbon and whereinsaid ash comprises less than about 5% of ash-carbon.

In an embodiment, the present disclosure provides a method for treatingsaid product gas at a temperature in about 1750° F. to about 3500° F. inthe presence of molecular oxygen to produce a raw syngas comprisingcarbon monoxide, hydrogen, and syngas-carbon. In various embodiments rawsyngas also comprises carbon dioxide.

In an embodiment, carbon to hydrogen mass ratio in one or more of saidcarbonaceous material comprises 1 to 20. In one embodiment carbon tooxygen mass ratio in one or more of said carbonaceous material comprises1 to 200.

As an embodiment, said raw-syngas comprises less than about 0.5 poundsyngas-carbon per 1000 SCF raw-syngas produced.

The present disclosure provides a method of gasification of carbonaceousmaterials in a gasifier to produce syngas using partial oxidationmethod; said gasifier comprising a first reaction zone and a secondreaction zone; said method comprising: adding one or more carbonaceousmaterials into said first reaction zone of gasifier; adding a molecularoxygen containing gas and optionally adding water or steam into one orboth of said first reaction zone and second reaction zone of saidgasifier; wherein amount of total oxygen added to said gasifier inpounds per pound of total carbon added to said gasifier comprisesgreater than about 1.25. In an embodiment amount of total oxygen addedinto said first reaction zone of said gasifier in pounds per pound oftotal carbon added to said gasifier comprises about 1.25 to about 3.5.In one embodiment said first reaction zone temperature comprises650-1450° F. In one embodiment said second reaction zone temperaturecomprises 1750-3500° F.

The present disclosure provides a method of gasification of carbonaceousmaterials in a gasifier to produce syngas; said gasifier comprising afirst reaction zone and a second reaction zone; said method comprising:adding one or more carbonaceous materials into said first reaction zoneof gasifier; adding a molecular oxygen containing gas and optionallyadding water or steam into one or both of said first reaction zone andsecond reaction zone of said gasifier; wherein amount of total oxygenadded to said gasifier in pounds per pound of total carbon added to saidgasifier comprises greater than about 1.25. In an embodiment amount oftotal oxygen added into said first reaction zone of said gasifier inpounds per pound of total carbon added to said gasifier comprises about1.25 to about 3.5. In one embodiment said first reaction zonetemperature comprises 650-1450° F. In one embodiment said secondreaction zone temperature comprises 1750-3500° F.

The present disclosure further provides a method comprising: subjectingsaid raw syngas to cooling and cleaning up to produce a clean syngas;contacting said clean syngas with a biocatalyst in a fermentationcontainer to produce an alcohol product mixture. In one embodimentcarbon to hydrogen mass ratio in one or more of said carbonaceousmaterials comprises 1 to 20. In one embodiment carbon to oxygen massratio in one or more of said carbonaceous materials comprises 1 to 200.

The present disclosure provides a method of gasification of carbonaceousmaterials in a gasifier to produce syngas using partial oxidationmethod; said gasifier comprising a first reaction zone, a secondreaction zone and a chamber connecting first reaction zone to secondreaction zone; said method comprising: adding one or more carbonaceousmaterials into said first reaction zone of gasifier; adding a molecularoxygen containing gas and optionally adding water or steam into one orboth of said first reaction zone and second reaction zone of saidgasifier; comprising adding molecular oxygen containing gas into saidchamber connecting said first reaction zone with said second reactionzone of said gasifier.

The present disclosure provides a gasifier to produce syngas usingpartial oxidation method; said gasifier comprising a first reactionzone, a second reaction zone and a chamber connecting first reactionzone to second reaction zone; said method comprising: adding one or morecarbonaceous materials into said first reaction zone of gasifier; addinga molecular oxygen containing gas and optionally adding water or steaminto one or both of said first reaction zone and second reaction zone ofsaid gasifier; comprising adding molecular oxygen containing gas intosaid chamber connecting said first reaction zone with said secondreaction zone of said gasifier.

The present disclosure provides a method of gasification of carbonaceousmaterials in a gasifier to produce syngas; said gasifier comprising afirst reaction zone, a second reaction zone and a chamber connectingfirst reaction zone to second reaction zone; said method comprising:adding one or more carbonaceous materials into said first reaction zoneof gasifier; adding a molecular oxygen containing gas and optionallyadding water or steam into one or both of said first reaction zone andsecond reaction zone of said gasifier; comprising adding molecularoxygen containing gas into said chamber connecting said first reactionzone with said second reaction zone of said gasifier.

The present disclosure provides a gasifier to produce syngas; saidgasifier comprising a first reaction zone, a second reaction zone and achamber connecting first reaction zone to second reaction zone; saidmethod comprising: adding one or more carbonaceous materials into saidfirst reaction zone of gasifier; adding a molecular oxygen containinggas and optionally adding water or steam into one or both of said firstreaction zone and second reaction zone of said gasifier; comprisingadding molecular oxygen containing gas into said chamber connecting saidfirst reaction zone with said second reaction zone of said gasifier.

In one embodiment of this disclosure the temperature of said gasifiercomprises about 650° F. to about 3500° F. In one embodiment thetemperature comprises about 650° F. to about 1450° F. In one embodimentthe temperature of said gasifier comprises about 950° F. to about 1400°F. In one embodiment the temperature of said gasifier is about 1400° F.In one embodiment the temperature of said gasifier comprises about 1750°F. to about 2250° F. In one embodiment the temperature of said gasifieris about 2250° F.

In various embodiments of the present disclosure said tar-containingproduct gas can be treated to remove or destroy at least a part of tarcontained in said tar-containing product gas using various tar removalmethods described in the published art in order to produce a tar-free orless tar-containing raw syngas. In one embodiment of the presentdisclosure said tar-containing product gas is treated at a temperatureof about 1750° F. to about 3500° F. in the presence of molecular oxygento remove or produce a raw syngas comprising carbon monoxide, hydrogen,and syngas-carbon. In one embodiment of the present disclosure saidtar-containing product gas is treated at a temperature of about 1750° F.to about 3500° F. in the presence of molecular oxygen to remove orproduce a raw syngas comprising carbon dioxide. Presumably in suchtreatment tar is destroyed through cracking of tar. Presumably in suchtreatment tar is destroyed through partial oxidation of tar. In oneembodiment the treatment temperature comprises about 1750° F. to about2250° F. In one embodiment the treatment temperature is about 2250° F.

Operation of gasifier as above does not accomplish complete combustionof all carbon introduced in the gasifier to produce carbon dioxide.Presumably a partial oxidation of carbon is accomplished that increasesproduction of carbon monoxide. Such partial oxidation may also lead toformation of un-reacted carbon particles or soot (“syngas-carbon”) thatremains in the raw syngas. Raw syngas containing large amount ofsyngas-carbon is undesirable as it increases difficulty and cost ofcleaning raw syngas. In the method of this disclosure said raw-syngascomprises less than about 0.5 pound syngas-carbon per 1000 SCFraw-syngas produced. In one embodiment of the disclosure, said rawsyngas comprises less than about 0.25 pound syngas-carbon per 1000 SCFraw syngas produced. In one embodiment, said raw syngas comprises lessthan about 0.125 pound syngas-carbon per 1000 SCF raw syngas produced.

Operation of gasifier as above does not accomplish complete combustionof all carbon introduced in the gasifier to produce carbon dioxide.Presumably an incomplete oxidation of carbon is accomplished thatincreases production of carbon monoxide. Such incomplete oxidation mayalso lead to formation of un-reacted carbon particles or soot(“syngas-carbon”) that remains in the raw syngas. Raw syngas containinglarge amount of syngas-carbon is undesirable as it increases difficultyand cost of cleaning raw syngas. In the method of this disclosure saidraw-syngas comprises less than about 0.5 pound syngas-carbon per 1000SCF raw-syngas produced. In one embodiment of the disclosure, said rawsyngas comprises less than about 0.25 pound syngas-carbon per 1000 SCFraw syngas produced. In one embodiment, said raw syngas comprises lessthan about 0.125 pound syngas-carbon per 1000 SCF raw syngas produced.

Gasification of carbonaceous materials to produce tar-containing productgas and subsequent treatment of said tar-containing product gas at hightemperature in the presence of molecular oxygen containing gas (“tarcracking”) to produce tar-free or less-tar-containing raw syngas can beaccomplished in multiple and separate process units or in a single unitwith multiple reaction zones or chambers or compartments.

Gasification of carbonaceous materials to produce tar-containing productgas and subsequent treatment of said tar-containing product gas at hightemperature in the presence of molecular oxygen containing gas (“partialoxidation of tar”) to produce tar-free or less-tar-containing raw syngascan be accomplished in multiple and separate process units or in asingle unit with multiple reaction zones or chambers or compartments.

In one embodiment of the instant disclosure, a gasification unit is usedthat comprises two reaction zones: a first reaction zone that produces atar-containing product gas and a second reaction zone that producestar-free or less-tar-containing raw syngas from tar-containing productgas.

In one embodiment of the instant disclosure, a multi-stage gasificationunit is used that comprises two reaction zones: a first reaction zonethat produces a tar-containing product gas and a second reaction zonethat produces tar-free or less-tar-containing raw syngas fromtar-containing product gas.

In one embodiment of the instant disclosure, a two-stage gasificationunit is used that comprises two reaction zones: a first reaction zonethat produces a tar-containing product gas and a second reaction zonethat produces tar-free or less-tar-containing raw syngas fromtar-containing product gas.

In one embodiment of the present disclosure temperature in the firstreaction zone should not be above the melting point of the inorganiccomponents of the carbonaceous materials that form ash. This temperaturemight be called ash-fusion temperature. In one embodiment, the firstreaction zone is maintained at a temperature of about 650° F. to about1450° F. In one embodiment, the first reaction zone is maintained at atemperature of about 950° F. to about 1450° F. In one embodiment, thefirst reaction zone is maintained at a temperature of about 1400° F.

Temperature in the second reaction zone should be high enough fortar-cracking to occur effectively. In one embodiment, the secondreaction zone is maintained at a temperature of about 1750° F. to about3500° F. In one embodiment, the second reaction zone is maintained at atemperature of about 1750° F. to about 2250° F. In one embodiment, thesecond reaction zone is maintained at a temperature of about 2250° F. Inaddition to maintaining appropriate temperature, the second reactionzone should be sized in a way that an appropriate contact time orresidence time is provided for tar-cracking. Typically a residence timeof about 2 to about 5 seconds is maintained.

Temperature in the second reaction zone should be high enough forpartial oxidation to occur effectively. In one embodiment, the secondreaction zone is maintained at a temperature of about 1750° F. to about3500° F. In one embodiment, the second reaction zone is maintained at atemperature of about 1750° F. to about 2250° F. In one embodiment, thesecond reaction zone is maintained at a temperature of about 2250° F. Inaddition to maintaining appropriate temperature, the second reactionzone should be sized in a way that an appropriate contact time orresidence time is provided for tar-cracking. Typically a residence timeof about 2 to about 5 seconds is maintained.

In one embodiment, the second reaction zone is placed vertically abovethe first reaction zone. In one embodiment, the second reaction zone isplaced vertically below the first reaction zone.

Molecular oxygen containing gas is added in the first reaction zone ofsaid gasifier. Molecular oxygen containing gas is added in the secondreaction zone of said gasifier. Molecular oxygen containing gas is addedin both the first and the second reaction zones of said gasifier.Molecular oxygen containing gas can be air, oxygen-enriched air or pureoxygen. Molecular oxygen containing gas may contain from about 21 volume% to about 100 volume % molecular oxygen.

In this disclosure, total oxygen added in gasifier is the sum of oxygencontent of the one or more carbonaceous materials added into gasifier,oxygen contained in any optionally added water or steam, and oxygencontained in molecular oxygen containing gas injected in both the firstreaction zone or lower and the second reaction zone or upper chamber ofthe gasifier; total carbon added in gasifier is the sum of carboncontent of one or more carbonaceous materials added into gasifier.

In this disclosure, total oxygen added in first reaction zone ofgasifier is the sum of oxygen content of one or more carbonaceousmaterials added in the first reaction zone of gasifier, oxygen containedin any optionally added water or steam in the first reaction zone ofgasifier, and oxygen contained molecular oxygen containing gas added infirst reaction zone of the gasifier; total carbon added in firstreaction zone of gasifier is the sum of carbon content of one or morecarbonaceous materials added in the first reaction zone of gasifier.

In one embodiment total carbon added in the first reaction zone ofgasifier is equal to total carbon added in gasifier.

In one embodiment total carbon added in the first reaction zone ofgasifier is not equal to total carbon added in gasifier.

As an embodiment, the present disclosure also provides method ofproducing alcohol comprising:

subjecting said raw syngas to cooling and cleaning up to produce a cleansyngas;

contacting said clean syngas with a biocatalyst in a fermentationcontainer to produce an alcohol product mixture.

In one embodiment, one or more said alcohols comprises methanol. In oneembodiment, one or more said alcohols comprises ethanol. In oneembodiment, one or more said alcohols comprises methanol, ethanol,propanol, butanol, and their combinations.

In one embodiment an alcohol is selectively recovered from the alcoholproduct mixture. In one embodiment, the alcohol selectively recovered isethanol. In one embodiment, the alcohol selectively recovered isbutanol.

As an embodiment, said biocatalyst comprises: microoganisms; acetogenicbacteria; one or more strains selected from Clostridium, Moorella, andCarboxydothermus or their mixed strains; Clostridium ljungdahlii. SaidClostridium ljungdahlii of the present disclosure is selected from thestrains consisting of PETC, ERI-2, O-52 and C-01 or their combinations.

FIG. 1 comprises a schematic diagram illustrating an embodiment of agasifier. FIG. 1 presents a schematic diagram of a two-stage gasifier.As an embodiment, FIG. 1 presents a schematic diagram of a two-stagegasifier using partial oxidation. Referring now to FIG. 1, one or morecarbonaceous materials (150) is fed from a feed hopper (100) to thefirst reaction zone or lower chamber (200) of the gasifier forgasification. Molecular oxygen containing gas (220) is introduced intothe lower chamber for assisting gasification. In one embodiment, wateror steam can be added in the lower chamber to assist gasification.Amount of oxygen injected in the lower chamber is regulated in a way toprevent complete combustion of the carbonaceous material. In otherwords, the lower chamber is oxygen-starved. Prevention of completecombustion is also regulated by adjusting temperature in the lowerchamber. A temperature of 750 to 1450 degrees F. is maintained in thelower chamber. In one embodiment, the temperature in the lower chamberis adjusted in a way to prevent melting of any ash formed duringgasification. In one embodiment, the temperature in the lower chamber is1400 degrees F. In one embodiment, amount of molecular oxygen introducedin the lower chamber comprises 10 to 100 pound-moles per ton ofcarbonaceous material on a dry or water free basis.

A stream of gaseous material produced in the first reaction zone orlower chamber moves to the second reaction zone or upper chamber (400)of the gasifier via the chamber (300) connecting the first reactionzone/lower chamber to the second reaction zone/upper chamber. A streamof ash (250) is removed from the lower chamber. A stream of gaseousmaterial produced in the first reaction zone moves to the secondreaction zone (400) of the gasifier via the connecting chamber (300) ofthe gasifier connecting the first reaction zone to the second reactionzone. A stream of ash (250) is removed from the first reaction zone.

In an embodiment, steam can be added in first reaction zone/lowerchamber (200). In an embodiment, steam can be added in second reactionzone/upper chamber (400). In an embodiment, steam can be added in firstreaction zone/lower chamber (200) and second reaction zone/upper chamber(400). In an embodiment, steam can be added in chamber connecting firstreaction zone/lower chamber to second reaction zone/upper chamber. In anembodiment, steam can be added in gas stream (310) going to chamberconnecting first reaction zone/lower chamber to second reactionzone/upper chamber.

In an embodiment, continuous steam can be added in first reactionzone/lower chamber (200). In an embodiment, continuous steam can beadded in second reaction zone/upper chamber (400). In an embodiment,continuous steam can be added in first reaction zone/lower chamber (200)and second reaction zone/upper chamber (400). In an embodiment,continuous steam can be added in chamber (300) connecting first reactionzone/lower chamber to second reaction zone/upper chamber. In anembodiment, continuous steam can be added in gas stream (310) going tochamber connecting first reaction zone/lower chamber to second reactionzone/upper chamber.

Presumably partial oxidation of tar contained in the gaseous materialproduced in the lower chamber is accomplished in the upper chamber.Presumably cracking of tar contained in the gaseous material produced inthe lower chamber is accomplished in the upper chamber. A stream ofmolecular oxygen containing gas in introduced in the chamber connectingfirst reaction zone/lower chamber to second reaction zone/upper chamber(300) or throat of the gasifier in order to assist the partial oxidationand/or cracking of tar in the upper chamber. In one embodiment,molecular oxygen containing gas is introduced directly inside the upperchamber. Partial oxidation of tar is also regulated by adjusting thetemperature in the upper chamber of the gasifier. Cracking of tar isalso regulated by adjusting the temperature in the upper chamber of thegasifier. A temperature of 1750 to 3500 degrees F. is maintained in theupper chamber. In one embodiment, the temperature in the upper chamberis 2250 degrees F. In one embodiment, amount of molecular oxygenintroduced in the upper chamber comprises 10 to 100 pound-moles per tonof carbonaceous material on a dry or water free basis.

In one embodiment, the upper chamber is positioned at a level verticallyabove the top of the lower chamber. In one embodiment, the upper chamberis positioned at a level not vertically above the top of the lowerchamber. In one embodiment, the lower chamber and upper chamber arepositioned at about the same vertical elevation, i.e. side by side. Astream of raw syngas (410) is removed from the upper chamber of thegasifier.

FIG. 2 comprises a schematic diagram illustrating an embodiment of aprocess to produce ethanol from a carbonaceous material via gasificationof said carbonaceous material. Referring now to FIG. 2, a carbonaceousmaterial (1) is fed into a gasifier (10) wherein the carbonaceousmaterial is converted to producer gas or synthesis gas or syngascomprising carbon monoxide (CO) and hydrogen (H₂). A raw syngas product(11) is removed from the gasifier. The raw syngas is hot and it maycontain sulfur-containing gas and other acidic gases, particulatematerial, etc and is subjected to cooling and clean up in a cooling andclean-up process (20). A cooled and cleaned up stream of syngas (21) isproduced by the cooling and clean-up process that is introduced in abioreactor or fermenter or fermentor (30) to produce ethanol. In thebioreactor carbon monoxide (CO) and hydrogen (H₂) of syngas is acted onby microorganisms to produce ethanol. An ethanol containing stream (31)is removed from the bioreactor. The ethanol containing stream can befurther processed to produce fuel grade ethanol (not shown in diagram).

FIG. 3 comprises a schematic diagram illustrating an embodiment of theeffect of total oxygen input into gasifier on syngas-carbon for variousamounts of water input into gasifier. As an embodiment, FIG. 3illustrates that trend of total syngas-carbon content decreases as thetotal oxygen input into gasifier increases. FIG. 3 is a plot of syngascarbon in pounds per KSCF of raw syngas produced (y-axis) versus totaloxygen input in pounds per pound total carbon input (x-axis). FIG. 3 isa plot of syngas carbon in pounds per thousand SCF of raw syngasproduced (y-axis) versus total oxygen input in pounds per pound totalcarbon input (x-axis). FIG. 3 is a plot of syngas carbon in pounds perthousand SCF of raw syngas produced (y-axis) versus total oxygen inputin pounds per pound total carbon input (x-axis); wherein total oxygeninput is total oxygen input into gasifier and total carbon input istotal carbon input into gasifier. For a total oxygen input into gasifiergreater than about 1.4 pound per pound (lb/lb) total carbon input intogasifier, raw syngas comprises less than about one (1) pound (lb)syngas-carbon per one thousand standard cubic feet (1000 SCF or KSCF) ofraw syngas produced. For a total oxygen input into the gasifier greaterthan about 1.5 pound per pound (lb/lb) total carbon input into gasifier,raw syngas comprises less than about 0.3 pound (lb) syngas-carbon perone thousand standard cubic feet (1000 SCF or KSCF) of raw syngasproduced.

FIG. 4 comprises a schematic diagram illustrating an embodiment of theeffect of total oxygen input into gasifier on amount of ethanol producedfor various amounts of water input into gasifier. As an embodiment, FIG.4 illustrates that trend of alcohol production initially increases withthe increase in total oxygen input. FIG. 4 is a plot of ethanol producedin pounds per pound total carbon input (y-axis) versus total oxygeninput in pounds per pound total carbon input (x-axis). FIG. 4 is a plotof ethanol produced in pounds per pound total carbon input (y-axis)versus total oxygen input in pounds per pound total carbon input(x-axis); wherein total oxygen input is total oxygen input into gasifierand total carbon input is total carbon input into gasifier. As anembodiment, FIG. 4 illustrates that trend of alcohol productioninitially increases with the increase in total oxygen input and thendecreases with increase in total oxygen input. As an embodiment, FIG. 4illustrates that trend of ethanol production initially increases withthe increase in total oxygen input. As an embodiment, FIG. 4 illustratesthat trend of ethanol production initially increases with the increasein total oxygen input and then decreases with increase in total oxygeninput. As an embodiment, FIG. 4 illustrates that trend of ethanolproduction (pounds ethanol produced per pound of total carbon input intogasifier) increases with the increase in total oxygen input intogasifier up to total oxygen input of about one and a half (1.5) poundper pound (lb/lb) total carbon input into gasifier. As an embodiment,FIG. 4 illustrates that trend of ethanol production (pounds ethanolproduced per pound of total carbon input into gasifier) increases withthe increase in total oxygen input into gasifier up to total oxygeninput of about one and a half (1.5) pound per pound (lb/lb) total carboninput into gasifier and for total oxygen input into gasifier above oneand a half (1.5) pound per pound (lb/lb) total carbon input intogasifier, ethanol production (pounds ethanol produced per pound of totalcarbon input into gasifier) decreases with increase in total oxygeninput into gasifier.

FIG. 5 comprises a schematic diagram illustrating an embodiment of theeffect of total oxygen input into first reaction zone of gasifier onsyngas-carbon for various amounts of water input into gasifier. As anembodiment, FIG. 5 illustrates that trend of total syngas-carbon contentof raw syngas decreases as the total oxygen input into first reactionzone of gasifier increases. FIG. 5 is a plot of syngas carbon in poundsper KSCF of raw syngas produced (y-axis) versus total oxygen input intofirst reaction zone in pounds per pound total carbon input (x-axis).FIG. 5 is a plot of syngas carbon in pounds per thousand SCF of rawsyngas produced (y-axis) versus total oxygen input into first reactionzone in pounds per pound total carbon input (x-axis). FIG. 5 is a plotof syngas carbon in pounds per thousand SCF of raw syngas produced(y-axis) versus total oxygen input into first reaction zone in poundsper pound total carbon input (x-axis); wherein total oxygen input intofirst reaction zone is total oxygen input into first reaction zone ofgasifier and total carbon input is total carbon input into gasifier. Fora total oxygen input into first reaction zone of the gasifier greaterthan about 0.75 pound per pound (lb/lb) total carbon input intogasifier, raw syngas comprises less than about one (1) pound (lb)syngas-carbon per one thousand standard cubic feet (1000 SCF) of rawsyngas produced. For a total oxygen input into first reaction zone ofgasifier greater than about 0.9 pound per pound (lb/lb) total carboninput into gasifier, raw syngas comprises less than about 0.3 pound (lb)syngas-carbon per one thousand standard cubic feet (1000 SCF or KSCF) ofraw syngas produced.

FIG. 6 comprises a schematic diagram illustrating an embodiment of theeffect of total oxygen input into first reaction zone of gasifier onamount of ethanol produced for various amounts of water input intogasifier. As an embodiment, FIG. 6 illustrates that trend of alcoholproduction initially increases with increase in total oxygen input intofirst reaction zone of gasifier. FIG. 6 is a plot of ethanol produced inpounds per pound total carbon input (y-axis) versus total oxygen inputin first reaction zone in pounds per pound total carbon input (x-axis).FIG. 6 is a plot of ethanol produced in pounds per pound total carboninput (y-axis) versus total oxygen input first reaction zone in poundsper pound total carbon input (x-axis); wherein total oxygen input firstreaction zone is total oxygen input into first reaction zone of gasifierand total carbon input is total carbon input into gasifier. As anembodiment, FIG. 6 illustrates that trend of alcohol productioninitially increases with the increase in total oxygen input into firstreaction zone of gasifier and then decreases with increase in totaloxygen input into first reaction zone of gasifier. As an embodiment,FIG. 6 illustrates that trend of ethanol production initially increaseswith the increase in total oxygen input into first reaction zone ofgasifier. As an embodiment, FIG. 6 illustrates that trend of ethanolproduction initially increases with the increase in total oxygen inputinto first reaction zone of gasifier and then decreases with increase intotal oxygen input into first reaction zone of gasifier. As anembodiment, FIG. 6 illustrates that trend of ethanol production (poundsethanol produced per pound of total carbon input into gasifier)increases with the increase in total oxygen input into first reactionzone of gasifier up to total oxygen input into first reaction zone ofgasifier of about 0.9 pound per pound (lb/lb) total carbon input intogasifier. As an embodiment, FIG. 6 illustrates that trend of ethanolproduction (pounds ethanol produced per pound of total carbon input intogasifier) increases with the increase in total oxygen input into firstreaction zone of gasifier up to total oxygen input into first reactionzone of gasifier of about 0.9 pound per pound (lb/lb) total carbon inputinto gasifier and for total oxygen input into first reaction zone ofgasifier above 0.9 pound per pound (lb/lb) ethanol production (poundsethanol produced per pound of total carbon input into gasifier),decreases with increase in total oxygen input into first reaction zoneof gasifier.

The foregoing descriptions of specific embodiments of the presentdisclosure are presented for purposes of illustration and description.They are not intended to be exhaustive or to limit the disclosure to theprecise forms disclosed. Obviously, many modifications and variationsare possible in view of the above teachings. While the embodiments werechosen and described in order to best explain the principles of thedisclosure and its practical applications, thereby enabling othersskilled in the art to best utilize the disclosure, various embodimentswith various modifications as are suited to the particular use are alsopossible.

In one embodiment of this disclosure alcohol is produced by contactingsyngas with biocatalyst in a fermentation container to produce analcohol product mixture. In one embodiment said alcohol comprisesmethanol, ethanol, propanol, and butanol or their combinations. In oneembodiment said alcohol comprises ethanol. In one embodiment saidbiocatalyst comprises acetogenic bacteria. In one embodiment saidbiocatalyst comprises one or more strains selected from Clostridium,Moorella, and Carboxydothermus or their mixed strains. In one embodimentsaid biocatalyst comprises one or more strains of Clostridiumljungdahlii. In one embodiment said Clostridium ljungdahlii is selectedfrom the strains consisting of PETC, ERI-2, O-52 and C-01 or theircombinations. In one embodiment said biocatalyst comprises one or morestrains of Clostridium carboxidivorans. In one embodiment saidbiocatalyst comprises one or more strains of Clostridium ragsdalei. Inone embodiment said biocatalyst comprises one or more strains ofClostridium autoethanogenum.

EXAMPLES

A multistage gasifier is contemplated in the present disclosure. As anembodiment, a multistage gasifier using partial oxidation method iscontemplated in the present disclosure. The following examples utilize atwo stage gasifier as shown in FIG. 1. The gasifier comprises a firststage or first reaction zone or lower chamber and a second stage orsecond reaction zone or upper chamber. Carbonaceous material is fed tothe lower chamber in which air, oxygen-enriched air or pure oxygen canbe injected at a controlled rate below a grate. For the examplespresented below, pure oxygen is injected in the lower chamber. The lowerchamber temperature and oxygen input is controlled such that onlyincomplete oxidation of carbonaceous material occurs, not completecombustion (also described as starved air or starved oxygen combustion).The lower chamber temperature and oxygen input is controlled such thatonly partial oxidation of carbonaceous material occurs, not completecombustion (also described as starved air or starved oxygen combustion).A temperature of about 750 to about 1450 degrees F. is maintained in thelower chamber. In one embodiment, a temperature of about 1400 degrees F.is maintained in the first stage. In one embodiment, a temperature lessthan about 1400 degrees F. is maintained in the first stage or lowerchamber. The gaseous product from the lower chamber moves to the secondstage or upper chamber. Ash is removed from the lower chamber. Pureoxygen is introduced into the upper chamber to raise the temperature toan upper chamber temperature of about 1750 to about 3500 degrees F. inorder to accomplish cracking of any tar (such as heavy hydrocarbons)contained in the gaseous stream from the first stage. Pure oxygen isintroduced into the upper chamber to raise the temperature to an upperchamber temperature of about 1750 to about 3500 degrees F. in order toaccomplish partial oxidation of any tar (such as heavy hydrocarbons)contained in the gaseous stream from the first stage. For the examplespresented below, the upper chamber temperature is 2250 degrees F. A rawproducer gas (also called raw synthesis gas or raw syngas) containingcarbon monoxide (CO), hydrogen (H₂) CO₂, N₂ and other constituents{e.g., O₂, particulate matter (PM), tars, metals} is produced andremoved from upper chamber. In one embodiment, steam can be injected inthe lower chamber. In an embodiment, steam can be injected in the upperchamber.

Following gasification, the raw syngas is subjected to cooling andcleanup to produce a product syngas. The product syngas is introduced ina bioreactor or fermentor or fermenter to produce alcohols; methanol;ethanol; propanol; and/or butanol. In the examples below, ethanol isproduced in the bioreactor.

In the examples below mathematical models were used to calculate theoutput of gasifier and fermenter for various process conditions and feedmaterials in lieu of actual experimentation. For calculation of gasifieroutput, a CHEMKIN mathematical model based was used.

The model used a 5% air leakage into the lower chamber or first reactionzone of the gasifier.

The model for the fermentation process involves a process that converts90% carbon monoxide and a process that converts 40% hydrogen with 95%selectivity for each process to make ethanol.

Examples 1-29

Examples 1-29 exemplify embodiment of gasification of carbonaceousmaterials containing no or negligible water and no water or steamdirectly added to gasifier as well as embodiment of gasification ofcarbonaceous materials containing substantial water and/or substantialamount of water or steam directly added to gasifier. The examplesexemplify embodiments of gasification of single carbonaceous materialssuch as coal, coke oven tar (coke), plastic, tire, wood, polystyrene(PS), polyethylene terephthalate (PETA) and plurality of carbonaceousmaterial such as blends of tire and wood, plastic and wood, plastic andmsw, and coke oven tar and fibersoft. For all these examples, thetemperature in the first reaction zone is 1400° F. and the temperaturein the second reaction zone is 2250° F. Relevant carbonaceous materialproperties, other gasification conditions and product data aresummarized in Table I and Table II below.

As embodiments, following are descriptions of blends of carbonaceousmaterials shown in examples 1-29:

Biomass-VW-15: blend of 80 wt % biomass and 20 wt % construction woodwaste or vegetative waste with a 15 wt % water content of the blend

Coke-fibersoft-10: blend of 50 wt % coke oven tar (coke) containing nowater and 50 wt % wet fibersoft containing 20 wt % water giving a 10 wt% water for the blend

Coke-fibersoft-20: blend of 50 wt % coke oven tar (coke) containing nowater and 50 wt % wet fibersoft containing 40 wt % water giving a 20 wt% water for the blend

Coke-fibersoft-30: blend of 50 wt % coke oven tar (coke) containing nowater and 50 wt % wet fibersoft containing 60 wt % water giving a 30 wt% water for the blend

Plastic-MSW-03: blend of 90 wt % plastic containing 0.2 wt % water and10 wt % MSW containing 30 wt % water giving a 3.2 wt % water for theblend

Plastic-MS W-08: blend of 75 wt % plastic containing 0.2 wt % water and25 wt % MSW containing 30 wt % water giving a 7.7 wt % water for theblend

Plastic-MSW-15: blend of 50 wt % plastic containing 0.2 wt % water and50 wt % MSW containing 30 wt % water giving a 15.1 wt % water for theblend

Plastic-wood-04: blend of 90 wt % plastic containing 0.2 wt % water and10 wt % wood containing 40 wt % water giving a 4.2 wt % water for theblend

Plastic-wood-10: blend of 75 wt % plastic containing 0.2 wt % water and25 wt % wood containing 40 wt % water giving a 10.2 wt % water for theblend

Plastic-wood-20: blend of 50 wt % plastic containing 0.2 wt % water and50 wt % wood containing 40 wt % water giving a 20.1 wt % water for theblend

Tire-wood-00: blend of 85 wt % tire containing no water and 15 wt % woodcontaining 40 wt % water and then pre-dried to remove all water

Tire-wood-03: blend of 85 wt % tire containing no water and 15 wt % woodcontaining 40 wt % water and then pre-dried to 3 wt % water content ofblend

Tire-wood-04: blend of 90 wt % tire containing no water and 10 wt % woodcontaining 40 wt % water giving a 4.0 wt % water for the blend

Tire-wood-06: blend of 85 wt % tire containing no water and 15 wt % woodcontaining 40 wt % water giving a 6.0 wt % water for the blend

Tire-wood-09: blend of 85 wt % tire containing no water and 15 wt % woodcontaining 40 wt % water and then added water to 9% water content ofblend

Tire-wood-10: blend of 75 wt % tire containing no water and 25 wt % woodcontaining 40 wt % water giving a 10 wt % water for the blend

Tire-wood-12: blend of 85 wt % tire containing no water and 15 wt % woodcontaining 40 wt % water and then added water to 15% water content ofblend

Tire-wood-15: blend of 85 wt % tire containing no water and 15 wt % woodcontaining 40 wt % water and then added water to 15% water content ofblend

TABLE I Properties of Carbonaceous Materials & Conditions ofGasification Processes for Examples 1-29 Feed Composition of FeedCarbonaceous Material Other Feed into Gasifier, Ex Carbonaceous CarbonOxygen Hydrogen Ash Other Water pound-moles/DT # Material wt % * wt % *wt % * wt % * wt % * wt % Steam O₂ (FZ) O₂ (SZ) 1 Biomass-VW-15 46.640.3 5.7 6.9 0.5 15.0 12.3 14.0 13.5 2 Coal 64.8 9.2 4.5 16.1 21.5 0.00.0 12.1 18.0 3 Coke-fibersoft-10 69.6 14.6 5.9 7.7 2.2 10.0 0.0 18.027.1 4 Coke-fibersoft-20 73.0 12.4 5.8 6.6 2.2 20.0 0.0 25.4 26.4 5Coke-fibersoft-30 77.5 9.7 5.7 5.1 2.0 30.0 0.0 33.9 25.3 6 Coke oventar 91.7 0.8 5.5 0.3 2.0 0.0 0.0 12.8 24.9 7 Plastic 73.0 10.6 9.5 3.46.9 0.2 0.0 24.3 29.8 8 Plastic-MSW-03 70.6 12.0 9.3 4.8 3.3 3.2 0.025.0 29.2 9 Plastic-MSW-08 66.8 14.3 8.9 7.0 3.0 7.7 0.0 27.0 26.7 10Plastic-MSW-15 59.4 18.5 8.2 11.3 2.6 15.1 0.0 26.3 21.0 11Plastic-wood-04 71.5 12.7 9.3 3.3 3.2 4.2 0.0 25.4 29.2 12Plastic-wood-10 69.1 16.1 8.9 3.1 2.8 10.2 0.0 27.0 26.7 13Plastic-wood-20 64.2 22.8 8.0 2.7 2.3 20.1 0.0 28.2 21.6 14 PETA 62.533.1 4.1 0.1 0.3 0.2 0.0 10.0 22.8 15 Polystyrene 86.8 3.9 8.4 0.5 0.90.2 0.0 30.7 30.7 16 Tire 64.2 4.4 5.0 25.6 26.4 0.0 0.0 11.5 16.8 17Tire 64.2 4.4 5.0 25.4 1.0 0.0 50.0 26.7 20.9 18 Tire 64.2 4.4 5.0 25.41.0 0.0 60.0 28.5 20.0 19 Tire 64.2 4.4 5.0 25.4 1.0 0.0 70.0 30.1 19.320 Tire-wood-00 62.8 8.1 5.0 23.1 24.1 0.0 0.0 11.3 17.7 21 Tire-wood-0362.8 8.1 5.0 23.1 1.0 3.0 0.0 13.4 19.9 22 Tire-wood-04 63.3 6.8 5.023.9 1.0 4.0 0.0 14.2 12.9 23 Tire-wood-06 62.8 8.1 5.0 23.1 1.0 6.0 0.015.4 27.2 24 Tire-wood-09 62.8 8.1 5.0 23.1 1.0 9.0 0.0 17.4 23.9 25Tire-wood-10 61.7 10.9 5.1 21.4 0.9 10.0 0.0 17.6 23.6 26 Tire-wood-1262.8 8.1 5.0 23.1 1.0 12.0 0.0 19.4 24.0 27 Tire-wood-15 62.8 8.1 5.023.1 0.1 15.0 0.0 21.4 23.3 28 Wood 49.5 43.1 5.4 1.5 2.0 0.0 0.0 6.317.4 29 Wood 49.5 43.1 5.5 1.5 0.4 40.0 0.0 24.5 13.3 NOTE: * indicatesdry or water free basis; DT means ton of dry or water freecarbonaceousmaterial

TABLE II Products of Gasification & Subsequent Fermentation Processesfor Examples 1-29 Raw Syngas Components Produced, pound-moles/DT RawSyngas Ash-Carbon, Ethanol, Ex Syngas- Volume, pound- pound- # Feed COH₂ CO₂ H₂O Carbon KSCF/DT moles/DT moles /DT 1 Biomass-VW-15 59.1 49.317.9 38.8 0.1 60321 0.574 11.5 2 Coal 67.5 42.7 0.1 0.1 38.9 55782 1.34012.3 3 Coke-fibersoft-10 108.9 67.8 1.6 2.6 4.8 68505 0.942 19.8 4Coke-fibersoft-20 112.6 72.7 7.5 12.6 1.1 76228 0.546 20.6 5Coke-fibersoft-30 113.0 77.4 15.2 27.0 0.5 86109 0.422 21.0 6 Coke oventar 77.9 61.2 0.1 0.1 74.9 78465 0.025 15.0 7 Plastic 111.2 93.1 0.8 1.99.4 79625 0.284 21.7 8 Plastic-MSW-03 111.4 91.5 2.1 4.5 3.8 78546 0.39921.7 9 Plastic-MSW-08 104.4 87.1 4.9 10.6 1.4 76746 0.586 20.4 10Plastic-MSW-15 87.4 77.4 10.2 23.5 0.5 73293 0.942 17.4 11Plastic-wood-04 112.3 91.7 2.6 5.4 3.2 79187 0.284 21.8 12Plastic-wood-10 107.5 87.9 6.2 13.2 1.2 79482 0.266 20.9 13Plastic-wood-20 92.8 78.1 13.6 29.7 0.4 78874 0.225 18.2 14 PETA 98.640.1 1.4 1.5 4.4 53409 0.004 16.6 15 Polystyrene 118.7 83.9 0.4 0.6 25.884425 0.038 22.2 16 Tire 58.2 49.4 0.0 0.1 46.8 56564 2.098 11.4 17 Tire91.4 72.5 13.1 27.0 0.4 75191 2.098 17.6 18 Tire 88.3 74.0 16.3 35.5 0.378833 2.098 17.3 19 Tire 85.3 75.3 19.3 44.2 0.2 82470 2.098 16.9 20Tire-wood-00 64.1 49.9 0.1 0.1 38.6 55973 1.924 12.3 21 Tire-wood-0375.3 53.2 0.1 0.2 27.4 57335 1.924 14.1 22 Tire-wood-04 77.1 54.0 0.10.3 26.3 57949 1.990 14.4 23 Tire-wood-06 86.4 56.6 0.3 0.5 16.0 587791.924 15.9 24 Tire-wood-09 95.2 59.6 0.9 1.4 6.6 60300 1.924 17.3 25Tire-wood-10 95.8 59.5 2.0 3.2 3.0 60202 2.168 17.4 26 Tire-wood-12 97.761.2 2.4 3.9 2.6 61867 1.924 17.8 27 Tire-wood-15 96.9 62.2 4.4 7.4 1.463527 1.924 17.7 28 Wood 75.8 44.9 6.7 10.2 0.6 50387 0.127 13.6 29 Wood48.7 46.2 33.6 82.9 0.0 77345 0.127 9.9

All published documents are incorporated by reference herein. Numerousmodifications and variations of the present disclosure are included inthe above-identified specification and are expected to be obvious to oneof skill in the art. Such modifications and alterations to thecompositions and methods of the present disclosure are believed to beencompassed in the scope of the claims appended hereto. Accordingly,various modifications, adaptations, and alternatives can occur to oneskilled in the art without departing from the spirit and scope herein.

1. A non-catalytic gasifier to produce syngas wherein said gasifierproduces a product gas comprising carbon monoxide, hydrogen, and tar;said method comprising: adding one or more carbonaceous materials,adding a molecular oxygen-containing gas and optionally adding waterinto said gasifier; wherein amount of total oxygen added to saidgasifier in pounds per pound of total carbon added to said gasifiercomprises greater than 2.0 and less than about 3.0; wherein the gasifierproduces ash comprising ash-carbon and wherein said ash comprises lessthan about 10% of ash-carbon; wherein said product gas is treated at atemperature of about 1750° F. to about 3500° F. in the presence ofmolecular oxygen to produce a raw-syngas comprising carbon monoxide,hydrogen, and syngas-carbon; wherein said raw-syngas comprises less thanabout 0.5 pound syngas-carbon per 1000 SCF raw-syngas produced; whereinsaid product gas comprises CO to CO₂ ratio greater than 1.4; and whereinsaid raw-syngas volume ranges from 50387 to 86109 KSCF/DT.
 2. (canceled)3. The gasifier of claim 1 comprising water addition to said gasifier.4. The gasifier of claim 1 comprising direct steam addition into saidgasifier.
 5. The gasifier of claim 1 comprising water addition bypartial direct steam addition into said gasifier.
 6. The gasifier ofclaim 1 comprising adding one or more said carbonaceous materialscontaining moisture into said gasifier.
 7. The gasifier of claim 1wherein one or more said carbonaceous materials comprises selection fromcarbonaceous material, carbonaceous liquid product, industrialcarbonaceous liquid recycle, carbonaceous municipal solid waste (MSW),carbonaceous urban waste, carbonaceous agricultural material,carbonaceous forestry material, carbonaceous wood waste, carbonaceousconstruction material, carbonaceous vegetative material, carbonaceouspetrochemical coproducts, carbonaceous coal, plastic, waste plastic,coke oven tar, fibersoft, tires, lignin, black liquor, polymers, wastepolymers, polyethylene terephthalate (PETA), polystyrene (PS), sewagesludge, animal waste, crop residues, energy crops, forest processingresidues, wood processing residues, livestock wastes, poultry wastes,food processing residues, fermentative process wastes carbonaceousindustrial waste, alcohol production wastes, ethanol coproducts, spentgrains, spent microorganisms or their combinations.
 8. The gasifier ofclaim 1 wherein carbon content of one or more said carbonaceousmaterials comprises about 0.25 to about 1.0 pounds per pound of one ormore said carbonaceous materials on a water free basis.
 9. The gasifierof claim 1 wherein hydrogen content of one or more said carbonaceousmaterials comprises about 0.0 to about 0.25 pounds per pound of one ormore said carbonaceous materials on a water free basis.
 10. The gasifierof claim 1 wherein oxygen content of one or more said carbonaceousmaterials comprises about 0.0 to about 0.5 pounds per pound of one ormore said carbonaceous materials on a water free basis.
 11. (canceled)12. The gasifier of claim 1 wherein the gasifier produces ash comprisingash-carbon and wherein said ash comprises less than about 5% ofash-carbon.
 13. (canceled)
 14. The gasifier of claim 1, wherein carbonto hydrogen mass ratio in one or more of said carbonaceous materialscomprises 1 to
 20. 15. The gasifier of claim 1, wherein carbon to oxygenmass ratio in one or more of said carbonaceous materials comprisesgreater than about 1 to about
 200. 16. (canceled)
 17. A non-catalyticgasifier to produce raw-syngas; said gasifier comprising a firstreaction zone and a second reaction zone; comprising: adding one or morecarbonaceous materials into said first reaction zone of gasifier; addinga molecular oxygen containing gas and optionally adding water or steaminto one or both of said first reaction zone and second reaction zone ofsaid gasifier; wherein amount of total oxygen added to said gasifier inpounds per pound of total carbon added to said gasifier comprisesgreater than 2.0 and less than about 3.0; wherein said raw-syngascomprises less than about 0.5 pound syngas-carbon per 1000 SCFraw-syngas produced; wherein said raw-syngas comprises CO to CO₂ ratiogreater than 1.4; and wherein said raw-syngas volume ranges from 50387to 86109 KSCF/DT.
 18. (canceled)
 19. The gasifier of claim 17 whereinsaid first reaction zone temperature comprises 650-1450° F.
 20. Thegasifier of claim 17 wherein said second reaction zone temperaturecomprises 1750-3500° F.
 21. The gasifier of claim 17 further comprising:subjecting said raw-syngas to cooling and cleaning up to produce a cleansyngas; contacting said clean syngas with a biocatalyst in afermentation container to produce an alcohol product mixture.
 22. Thegasifier of claim 17, wherein carbon to hydrogen mass ratio in one ormore of said carbonaceous materials comprises 1 to
 20. 23. The gasifierof claim 17, wherein carbon to oxygen mass ratio in one or more of saidcarbonaceous materials comprises 1 to
 200. 24. (canceled)
 25. (canceled)26. (canceled)
 27. (canceled)